[go: up one dir, main page]

CN101653736A - Method for synthesizing spherical granular carbon nano tube composite material - Google Patents

Method for synthesizing spherical granular carbon nano tube composite material Download PDF

Info

Publication number
CN101653736A
CN101653736A CN200910152667A CN200910152667A CN101653736A CN 101653736 A CN101653736 A CN 101653736A CN 200910152667 A CN200910152667 A CN 200910152667A CN 200910152667 A CN200910152667 A CN 200910152667A CN 101653736 A CN101653736 A CN 101653736A
Authority
CN
China
Prior art keywords
composite material
carbon nanotube
granular carbon
spherical granular
nanotube composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN200910152667A
Other languages
Chinese (zh)
Inventor
唐天地
胡珊
董雯华
郑亚芬
雷晓丽
陈俊
吴秋斌
傅雯倩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wenzhou University
Original Assignee
Wenzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wenzhou University filed Critical Wenzhou University
Priority to CN200910152667A priority Critical patent/CN101653736A/en
Publication of CN101653736A publication Critical patent/CN101653736A/en
Withdrawn legal-status Critical Current

Links

Images

Landscapes

  • Catalysts (AREA)

Abstract

本发明公开了一种球形颗粒状碳纳米管复合材料的合成方法，所述的合成方法是以大孔强碱性阴离子树脂为碳源，通过在大孔强碱性阴离子树脂上组装过渡金属离子，经干燥后，置于反应器中在化学惰性气体气氛下进行固相反应，得到所述的球形颗粒状碳纳米管复合材料；所述过渡金属为Fe、Co或Ni。本发明充分利用工业上易得的原材料，通过简单、经济的方法制备高附加值的碳纳米管小球复合材料，该材料具有高BET比表面积和大的介孔孔容，适于大规模生产。The invention discloses a synthesis method of a spherical granular carbon nanotube composite material. The synthesis method uses a macroporous strong basic anion resin as a carbon source, and assembles transition metal ions on the macroporous strong basic anion resin , after being dried, placed in a reactor to carry out solid-phase reaction under a chemically inert gas atmosphere to obtain the spherical granular carbon nanotube composite material; the transition metal is Fe, Co or Ni. The invention makes full use of industrially readily available raw materials to prepare high value-added carbon nanotube pellet composite materials through a simple and economical method. The material has high BET specific surface area and large mesoporous pore volume, and is suitable for large-scale production .

Description

A kind of synthetic method of form of spherical particles carbon nano tube compound material
(1) technical field
The present invention relates to a kind of synthetic method of form of spherical particles carbon nano tube compound material.
(2) background technology
Current material with carbon element such as active carbon are very wide in industrial application.Wherein especially with field of environment protection (as drinking water, Industrial Wastewater Treatment) consumption maximum.According to statistics, it is 151000 tons that the U.S. in 2000 is used for the active carbon in the environmental protection, accounts for 65% of active carbon output then, and the amount that wherein is used to handle industrial wastewater is 42000 tons.In the synthetic field of fine chemicals, active carbon also is the catalyst carrier of extensive use.But the micropore character of active carbon and relatively poor mechanical performance have also limited its application in some fields.Be difficult to realize big molecule organic pollutant adsorption in the industrial wastewater as active carbon; The catalyzed conversion that in fine chemicals is synthetic, also is difficult to realize macromolecular compound; The granular active carbon of making is also because of mechanical strength is lower, and generation powder easy to wear causes bed layer pressure to increase in fixed bed.
In recent years, with the synthetic CNT (CNT) of the whole bag of tricks graphite-structure, favorable mechanical performance, unique electric transmission character, suitable specific area and meso-hole structure are arranged.Help macromolecular diffusion, make it can substitute active carbon, have very tempting application prospect in environmental protection and catalytic field.Yet CNT can not have two in the industrial main cause of being applied so far: (1) CNT can't resemble at present and realize technical scale production the active carbon; (2) a little less than the inertia of CNT itself made itself and binding agent interact, the crushing strength of particle was not high after the moulding.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic method of form of spherical particles carbon nano tube compound material, and realization simply, extensive synthesizing has definite shape and particle size CNT composite economically.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of synthetic method of form of spherical particles carbon nano tube compound material, be to be carbon source with the macroporous strong basic resin anion (R.A.), by on the macroporous strong basic resin anion (R.A.), assembling transition metal ions, after drying, place reactor under chemically inactive gas atmosphere, to carry out solid phase reaction, obtain described form of spherical particles carbon nano tube compound material; Described transition metal is Fe, Co or Ni.
Macroporous strong basic resin anion (R.A.) of the present invention uses the commercial goods, and commercially available ion exchange resin is coccoid usually.The macroporous strong basic resin anion (R.A.) of the preferred following model of the present invention: D296, D201, D290 etc.
The form of spherical particles carbon nano tube compound material that the present invention makes has complete spherical morphology, has inherited the shape and the smooth surface (see figure 1) of raw material ion exchange resin bead.The size range of bead is compared volume-diminished at 0.4～0.5mm with the resin before the calcining.Fig. 2 is the stereoscan photograph of sample, sees significantly having generated a large amount of CNTs; Wherein the illustration in the upper left corner is the transmission electron microscope photo of sample, can clearly see the pattern of the CNT of generation.
The present invention recommended described solid phase reaction condition to be: 500～1200 ℃ of reactions 2～20 hours.Preferred solid phase reaction condition was: 600～1000 ℃ of reactions 3～6 hours.
The present invention can be by conventional method assembling metals on ion exchange resin such as ion-exchange or infusion processes.Because ion exchange resin itself just has tradable characteristic, so the present invention recommends to adopt ion-exchange to assemble transition metal ions on ion exchange resin.Concrete recommend described ion-exchange to carry out: the aqueous solution of macroporous strong basic resin anion (R.A.) and the complex anion that contains Fe, Co or Ni to be stirred exchange 2～20 hours, filter the macroporous strong basic resin anion (R.A.) bead that obtains being assembled with Fe, Co or Ni metal according to following.The complex anion of described Fe, Co or Ni is preferably the cyanogen complex ion of Fe, Co or Ni, as Hexacyanoferrate radical ion, six cyanogen close the cobalt acid ion, four cyanogen close nickel acid ion etc.Described macroporous strong basic resin anion (R.A.) can be D296, D201, D290 etc.
Above-mentioned ion-exchange, those skilled in the art can ion exchange resin according to actual needs on the assembling amount of metal determine the raw material rate of charge, concrete metal group loading amount can obtain by the following method: the form of spherical particles carbon nano tube compound material that makes is burned, the residue dissolving with hydrochloric acid carries out quantitatively with atomic absorption spectrum.
Among the present invention, the ratio of corresponding Fe, Co that contains in the aqueous solution of feed intake quality and the complex anion that contains Fe, Co or Ni of described macroporous strong basic resin anion (R.A.) or the quality of Ni is 1: 0.01～0.05, preferred 1: 0.01～0.03.The assembling amount that helps improving metal owing to the concentration of the complex anion of Fe, Co or Ni in the aqueous solution that improves the complex anion that contains Fe, Co or Ni, the molar concentration that the present invention recommends to contain the complex anion of Fe, Co in the aqueous solution of complex anion of Fe, Co or Ni or Ni is 0.02～0.07M, preferred 0.03～0.05M.
Solid phase reaction of the present invention, be under the chemically inactive gas atmosphere, to carry out, " chemically inactive gas " of indication of the present invention is except sense stricto inert gas, comprises that also nitrogen etc. does not participate in the gas of chemical reaction of the present invention, and the present invention is recommended under the nitrogen atmosphere and carries out.
Compared with prior art, beneficial effect of the present invention is:
A) the present invention makes full use of the industrial raw material that are easy to get, and prepares the CNT bead composite of high added value by simple, economic method.This material has high BET specific area (300～550m 2/ g), big mesoporous pore volume (0.3～0.5m 3/ g).Therefore, to be applied to packed bed as adsorbent or catalyst and carrier thereof very suitable industrial for this product.Can be widely used in field of environment protection such as Industrial Wastewater Treatment, air cleaning, and the catalyst or the catalyst carrier field that are used as fine chemicals.Be easy to utilize packed bed to realize producing continuously for the enterprise that uses this product, technical process is simple, equipment investment is few, operating cost is low.Therefore, its economical, societal benefits should be very remarkable.Our previous work shows that this product shows excellent catalytic activity and product selectivity as catalyst in the ethyl benzene dehydrogenation preparation of styrene reaction.
B) synthesis technique of this product is simple, less demanding to equipment, can realize that commercial scale produces in a large number.
(4) description of drawings
The optical microscope photograph of the form of spherical particles carbon nano tube compound material that Fig. 1 makes for the present invention.
Fig. 2 is the stereoscan photograph of sample, can see containing a large amount of CNTs in the sample; Wherein the illustration in the upper left corner is a transmission electron microscope photo, has clearly seen the pattern of the CNT that generates.
(5) specific embodiment
The invention will be further described below in conjunction with experimental subjects, but protection scope of the present invention is not limited to this.
The macroporous strong basic resin anion (R.A.) that the embodiment of the invention is used is the commercial goods, is coccoid.
Experimental example 1
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D296 joins 50ml is in the Hexacyanoferrate potassium solution of 0.03M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 500 ℃, calcine after 4 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 311m 2/ g, mesoporous pore volume 0.3m 3/ g.
Experimental example 2
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D201 joins 50ml is in the potassium hexacyanocobaltate solution of 0.04M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 500 ℃, calcine after 5 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 301m 2/ g, mesoporous pore volume 0.31m 3/ g.
Experimental example 3
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D290 joins 50ml is in the potassium tetracyanonickelate solution of 0.07M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 500 ℃, calcine after 5 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 318m 2/ g, mesoporous pore volume 0.33m 3/ g.
Experimental example 4
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D296 joins 50ml is in the Hexacyanoferrate potassium solution of 0.05M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 800 ℃, calcine after 3 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 490m 2/ g, mesoporous pore volume 0.38m 3/ g.
Experimental example 5
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D201 joins 50ml is in the potassium hexacyanocobaltate solution of 0.03M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 800 ℃, calcine after 3 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 486m 2/ g, mesoporous pore volume 0.41m 3/ g.
Experimental example 6
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D290 joins 50ml is in the potassium tetracyanonickelate solution of 0.02M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 800 ℃, calcine after 6 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 451m 2/ g, mesoporous pore volume 0.32m 3/ g.
Embodiment 7
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D296 joins 50ml is in the potassium hexacyanocobaltate solution of 0.05M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 1000 ℃, calcine after 2 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 501m 2/ g, mesoporous pore volume 0.44m 3/ g.
Experimental example 8
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D201 joins 50ml is in the potassium tetracyanonickelate solution of 0.03M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 1000 ℃, calcine after 3 hours, in the atmosphere also at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 516m 2/ g, mesoporous pore volume 0.45m 3/ g.
Experimental example 9
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D296 joins 50ml is in the potassium tetracyanonickelate solution of 0.04M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 1200 ℃, calcine after 2 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 552m 2/ g, mesoporous pore volume 0.52m 3/ g.
Experimental example 10
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D201 joins 50ml is in the Hexacyanoferrate potassium solution of 0.05M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 1200 ℃, calcine after 3 hours, in the atmosphere at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 534m 2/ g, mesoporous pore volume 0.59m 3/ g.
Experimental example 11
With quality is that the concentration that 4.00g macroporous strong basic resin anion (R.A.) D290 joins 50ml is in the potassium hexacyanocobaltate solution of 0.03M, stirs exchange 2 hours, filter, 80 ℃ dry down, again at N 2In the time of 1200 ℃, calcine after 5 hours, in the atmosphere also at N 2Be cooled to room temperature in the atmosphere.The specific area that obtains sample is 478m 2/ g, mesoporous pore volume 0.42m 3/ g.
Embodiment 12
It is the catalytic performance of catalyst in the ethyl benzene dehydrogenation preparation of styrene reaction that table 1 has provided respectively with the CNT bead composite of the iron content of embodiment 4 preparations, the CNT bead composite that contains cobalt of embodiment 5 preparations, the nickeliferous CNT bead composite of embodiment 6 preparations, in order to compare, also having provided is the load Fe catalyst of preparing carriers with the commercial carbon blacks.Reaction condition: be reflected on the atmospheric fixed bed reactor and carry out, 450 ℃ of reaction temperatures, 100mg catalyst, styrene charge flow are 8ml/h.
Wherein, the preparation method of commercial carbon blacks supported ferric catalyst is: adopt the method preparation of incipient impregnation, the mass fraction of Fe is 5%.
The catalytic performance of each catalyst is as shown in table 1, significantly, is the styrene productive rate height that catalyst obtains with CNT bead composite.
The catalytic performance of the iron catalyst of table 1.CNT bead composite and commercial carbon blacks load in the ethyl benzene dehydrogenation preparation of styrene reaction relatively
Figure A20091015266700101

Claims (9)

1、一种球形颗粒状碳纳米管复合材料的合成方法，所述的合成方法是以大孔强碱性阴离子树脂为碳源，通过在大孔强碱性阴离子树脂上组装过渡金属离子，经干燥后，置于反应器中在化学惰性气体气氛下进行固相反应，得到所述的球形颗粒状碳纳米管复合材料；所述过渡金属为Fe、Co或Ni。1, a kind of synthetic method of spherical granular carbon nanotube composite material, described synthetic method is to be carbon source with macroporous strong basic anion resin, by assembling transition metal ion on macroporous strong basic anion resin, through After drying, it is placed in a reactor for solid-phase reaction under a chemically inert gas atmosphere to obtain the spherical granular carbon nanotube composite material; the transition metal is Fe, Co or Ni. 2、如权利要求1所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述的固相反应条件为：在500～1200℃反应2～6小时。2. The synthesis method of spherical granular carbon nanotube composite material according to claim 1, characterized in that said solid phase reaction condition is: react at 500-1200°C for 2-6 hours. 3、如权利要求2所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述的固相反应条件为：在600～1000℃反应3～6小时。3. The synthesis method of spherical granular carbon nanotube composite material as claimed in claim 2, characterized in that said solid phase reaction condition is: react at 600-1000°C for 3-6 hours. 4、如权利要求1～3之一所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于通过离子交换法组装过渡金属离子，具体如下：将大孔强碱性阴离子树脂与含有Fe、Co或Ni的络合阴离子的水溶液搅拌交换2～10小时，过滤得到组装有Fe、Co或Ni离子的大孔强碱性阴离子树脂。4. The method for synthesizing the spherical granular carbon nanotube composite material according to any one of claims 1 to 3, characterized in that the transition metal ions are assembled by ion exchange method, specifically as follows: macroporous strong basic anion resin and containing The aqueous solution of complex anions of Fe, Co or Ni is stirred and exchanged for 2-10 hours, and filtered to obtain a macroporous strongly basic anion resin assembled with Fe, Co or Ni ions. 5、如权利要求4所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述的Fe、Co或Ni的络合阴离子为Fe、Co或Ni的氰络离子。5. The synthesis method of spherical granular carbon nanotube composite material according to claim 4, characterized in that the complex anions of Fe, Co or Ni are cyanide complex ions of Fe, Co or Ni. 6、如权利要求5所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述的Fe的络合阴离子为六氰合铁酸根离子，所述的Co的络合阴离子为六氰合钴酸根离子，所述的Ni的络合阴离子为四氰合镍酸根离子。6. The synthesis method of spherical granular carbon nanotube composite material as claimed in claim 5, characterized in that the complex anion of Fe is hexacyanoferrate ion, and the complex anion of Co is hexacyanoferrate ion. Cyanocobaltate ion, the complex anion of Ni is tetracyanonickelate ion. 7、如权利要求4所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述的大孔强碱性阴离子树脂的投料质量与含有Fe、Co或Ni的络合阴离子的水溶液中含有的相应的Fe、Co或Ni的质量之比为1∶0.01～0.05。7. The synthetic method of spherical granular carbon nanotube composite material as claimed in claim 4, characterized in that the quality of feeding of the macroporous strongly basic anion resin and the aqueous solution containing complex anions of Fe, Co or Ni The corresponding Fe, Co or Ni contained in the mass ratio is 1:0.01-0.05. 8、如权利要求7所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述含有Fe、Co或Ni的络合阴离子的水溶液中Fe、Co或Ni的络合阴离子的摩尔浓度为0.02～0.07M。8. The synthetic method of spherical granular carbon nanotube composite material as claimed in claim 7, characterized in that the mole of complex anions of Fe, Co or Ni in the aqueous solution containing complex anions of Fe, Co or Ni The concentration is 0.02～0.07M. 9、如权利要求1所述的球形颗粒状碳纳米管复合材料的合成方法，其特征在于所述的大孔强碱性阴离子树脂选自下列之一：D296、D201、D290。9. The synthesis method of spherical granular carbon nanotube composite material as claimed in claim 1, characterized in that said macroporous strongly basic anion resin is selected from one of the following: D296, D201, D290.
CN200910152667A 2009-09-17 2009-09-17 Method for synthesizing spherical granular carbon nano tube composite material Withdrawn CN101653736A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910152667A CN101653736A (en) 2009-09-17 2009-09-17 Method for synthesizing spherical granular carbon nano tube composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910152667A CN101653736A (en) 2009-09-17 2009-09-17 Method for synthesizing spherical granular carbon nano tube composite material

Publications (1)

Publication Number Publication Date
CN101653736A true CN101653736A (en) 2010-02-24

Family

ID=41708316

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910152667A Withdrawn CN101653736A (en) 2009-09-17 2009-09-17 Method for synthesizing spherical granular carbon nano tube composite material

Country Status (1)

Country Link
CN (1) CN101653736A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992306A (en) * 2012-11-14 2013-03-27 中山大学 Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof
CN109637826A (en) * 2018-12-14 2019-04-16 江苏科技大学 A kind of preparation method and applications of cobaltosic oxide-nickel oxide/grapheme foam combination electrode material
CN111468093A (en) * 2020-05-28 2020-07-31 沈阳师范大学 Preparation method of carbon nano tube monolithic catalyst
CN113955741A (en) * 2021-11-04 2022-01-21 浙江浙能技术研究院有限公司 A kind of preparation method and application of carbon nanotube macro-forming material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992306A (en) * 2012-11-14 2013-03-27 中山大学 Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof
CN102992306B (en) * 2012-11-14 2014-08-06 中山大学 Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof
CN109637826A (en) * 2018-12-14 2019-04-16 江苏科技大学 A kind of preparation method and applications of cobaltosic oxide-nickel oxide/grapheme foam combination electrode material
CN109637826B (en) * 2018-12-14 2020-09-08 江苏科技大学 Preparation method and application of cobaltosic oxide-nickel oxide/graphene foam composite electrode material
CN111468093A (en) * 2020-05-28 2020-07-31 沈阳师范大学 Preparation method of carbon nano tube monolithic catalyst
CN113955741A (en) * 2021-11-04 2022-01-21 浙江浙能技术研究院有限公司 A kind of preparation method and application of carbon nanotube macro-forming material

Similar Documents

Publication Publication Date Title
CN107486234B (en) Catalyst for preparing light aromatic hydrocarbon by directly converting synthesis gas and preparation method thereof
CN103170360B (en) Dimethyl ether carbonylation catalyst, and preparation method and application thereof
Mao et al. Fe-based MOFs@ Pd@ COFs with spatial confinement effect and electron transfer synergy of highly dispersed Pd nanoparticles for Suzuki-Miyaura coupling reaction
CN103506146B (en) Catalyst for decomposing hydrogen phosphide gas as well as preparation method and application thereof
WO2014008865A1 (en) Butadiene catalyst for fluidized bed reactor prepared by oxidizing and dehydrogenating butylene, and preparation method and use thereof
CN105396608A (en) A preformed catalyst used for a fixed-bed Fenton reaction and a preparing method thereof
CN110813296B (en) A kind of preparation method of nanoporous Ni-Fe alloy catalyst
CN107519872A (en) A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method
Yang et al. PdCo nanoparticles supported on carbon fibers derived from cotton: Maximum utilization of Pd atoms for efficient reduction of nitroarenes
CN108514863B (en) Method for preparing carbon-coated magnetic halloysite compound adsorbent by using humic acid and product obtained by method
CN110124743A (en) A kind of organic Pd catalyst of load type stephanoporate metal and its preparation method and application
CN111036232A (en) Composite metal oxide catalyst for catalytic combustion and preparation method thereof
CN105148937A (en) Magnetic graphene-loaded palladium nano-composite catalyst and preparation method thereof
CN104289222B (en) Catalyst supporting CuO on SiO2 for the preparation of quinone and p-benzoquinone and its preparation method
CN101653736A (en) Method for synthesizing spherical granular carbon nano tube composite material
CN106694004A (en) Loaded type transition metal phosphide catalyst and preparation method thereof
CN103977802A (en) Nano needle-like nickel-coated graphite compound particle and preparation method and application thereof
CN102921419B (en) A kind of for the direct hydroxylating of benzene Nanometer Copper-graphene composite catalyst preparing phenol and preparation method thereof
CN112844320A (en) Carbon material-coated spinel iron oxide in-situ growth MOFs adsorption catalysis complex and preparation method and application thereof
Lakshminarayana et al. Switching of support materials for the hydrogenation of nitroarenes: A review
CN110433802A (en) A kind of hydrogenation catalyst and preparation method thereof and the catalyst are used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare saturated aldehyde
Li et al. Predominant performance of a nitrogen-doped carbon confined NiCo alloy catalyst fabricated by a natural resource encapsulation strategy for tandem catalytic nitroarenes with alcohols
CN109928898A (en) A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green
CN110433827B (en) Magnetic catalyst, preparation method thereof and method for preparing furfuryl alcohol
CN105664946B (en) A kind of method for preparing solid phase of DCL/Direct coal liquefaction Fe-series catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C04 Withdrawal of patent application after publication (patent law 2001)
WW01 Invention patent application withdrawn after publication

Open date: 20100224